Resinous composition comprising epoxy resin, curing agent and mixture of dextrines, maltose and dextrose and process for preparing



Thomas Ramos, New York, NY.

No Drawing. Application February 12, 1957 Serial No. 639,624

9 Claims. (Cl. 260-9) This invention relates to resinous compositions,to a method of preparing said resinous compositions, and to wall andfloor coverings having a basis of said resinous compositions. Moreparticularly, this invention is concerned with improved resinouscompositions made from epoxy resins, which compositions, because oftheir unique properties, are especially useful as coverings for wallsand floors.

This application is a continuation-in-part of my application S. No.409,270, filed February 9, 1954, now abandoned.

It is well known to those familiar with the synthetic resin art thatmany useful resinous compositions have been prepared by the addition ofa curing or hardening agent to a resinous epoxide. The resin productsthus formed have been employed to prepare bonding, filmforming andcasting compositions useful in the manufacture of electrical devices,laminates, molded products and the like. In their final cured andhardened state the resin product, i.e. the epoxy resin, is crystallineand hard, having a Rockwell hardness of from M80 to M98 and even as highas M110, and a high rate of shear.

It is an important object of this invention to pre pare a resinouscomposition which has a basis of an epoxy resin but which haselastomeric characteristics, i.e. ranging from pliable, flexiblecompounds to compounds which have the characteristics of natural orsynthetic rubber.

Another object of this invention is the preparation of a resinouscomposition having a basis of an epoxy resin, which has a long pot life,even when worked in large bulk, and may be readily applied to a surfaceby trowelling, spraying or brush coating.

Still another object of this invention is the preparation ofa resinouscomposition having a basis of an epoxy resin, which may be cast in amold or otherwise formed into a self-supporting article havingelastomeric characteristics.

A further object of this invention is the preparation of a resinouscomposition having a basis of an epoxy resin, which may be readilytrowelled, sprayed or brush coated onto metal and non-metal surfaces toform protective coverings, e.g. walls or floors, which are firmly bondedto said surfaces, which are rubber-like in their mechanical propertiesand which are quite resistant to the action of water, heat, alkalies andacids, and to color-fading.

Other objects and advantages of this invention will appear from thefollowing description and claims.

in its broadest aspect, this invention contemplates the addition to amixture of resinous epoxide and a curing or hardening agent an additivecomprising a mix ture of saccharides, i.e. mono-, diand polysaccharides.The resultant mixture is agitated at room temperature inany suitablemixing or blending machine employing mechanical stirrers to produce anon-aqueous resinous composition which may be trowelled, sprayed orbrush "ice coated onto a metal or non-metal surface, such as a deck of aship, a floor of a pantry, galley, dairy, butcher shop, factory,warehouse, or other area subjected to wear or moist conditions, to forma long wearing protective surface thereon, and also onto walls to formwaterproof coatings thereon. An important feature of the resinouscomposition of this invention is that it readily bonds itself to themetal or non-metal surfaces, such as surfaces of ferrous and non-ferrousmetals, wood, wood laminates, concrete, latex mastic compositions,cementations compositions, fiber board, plastics, plastic laminates,ceramics, glass and the like without the use of wire mesh, clips orother mechanical fastening devices, or of special bonding agents. Theresinous compositions of this invention have a longer and morecontrollable pot life and Work life than the epoxy resin compositionscontaining a resinous epoxide and curing and hardening agent, but nomixture of saccharides. Because of the longer pot life and work lifelarger batches may be worked and thus larger areas may be covered withthe resinous compositions from a single batch. Moreover, the use of amixture of saccharides with the resinous epoxide and the curing orhardening agent has the effect of reducing the tendency of the mixtureto foam in the mixing apparatus, and lowers the exotherrn to F. andmore. Furthermore, the use of a mixture of saccharides with the resinousepoxide and curing or hardening agent produces a resinous composition orprotective covering which is quite different in mechanical propertiesfrom the hard, crystalline epoxy resins formed from resinous epoxidesand curing or hardening agents without the saccharides. 'Thus, theresinous products of this invention exhibit substantially no pin holes,cracks or crazing, have improved strength and a low rate of shear andhave the characteristics of an elastomer with respect to elasticity,flexibility, low shear strength and other physical properties.

More specifically, the elastomeric resinous compounds of this inventionare formed from resinous epoxides by adding to a resinous epoxide fromabout 7 to 15%, by weight of the resinous epoxide, of a curing orhardening agent and from about 6 to 10%, by weight of the resinousepoxide, of a mixture of saccharides, such as dextrins, a mixture ofdextrins and maltose, molasses or Karo syrup which is a mixture ofdextrins, maltose and dextrose, and mixing the three components togetherat room temperature to form a non-aqueous resinous composition.

The resinous epoxides employed in accordance with this invention arethose obtained by condensing polyhydric compounds, such as dihydricphenols, with polyfunctional halohydrins, such as epichlorohydr-in andglycerol epichlorhydrin. These resinous epoxides contain at least oneterminal 1, 2-epoxide group per molecule and are characterized by havingalternating aliphatic chains and aromatic nuclei united through etheroxygen. Such resinous epoxides are known as Ethoxyline resins (ChemicalWeek, September 8, 1951, vol. 69, page 27) and are chemically availableunder such trade names as Epon resins (Shell Chemical Corporation),Araldite resins (Ciba Company, Inc.) and Bakelite 0'8 resins (UnionCarbide & Carbon Corporation). Generally, such resinous epoxides containfrom one to two 1, Z-epoxide groups per molecule and have epoxideequivalents of from 30 to 4000. An example of the resinous epoxidesemployed in the present invention in the interest of workability is onehaving an epoxide equivalent no greater than 1000 and which is preparedby condensation of dihydroxy diphenyl dimethyl methane, especially,4,4'-dihydroxy diphenyl dimethyl methane, with epichlorhydrin. However,good results are obtained by the use of any of the resinous epoxides.

As curing or hardening agents for the resinous epoxides any of the wellknown substances for this purpose may be employed, such as, for example,alkalis like sodium or potassium hydroxide, alkali phenoxides,carboxylic acids or anhydrides thereof like formic acid, oxalic acid orphthalio anhydride, Friedel-Crafts metal halides like aluminum chloride,zinc chloride, ferric chloride or boron trifiuoride as well as complexesthereof with ethers, acid anhydrides, ketones, diazonium salts,phosphoric acid, and partial esters thereof, and amino compounds such astriethylamine, ethylene diamine, diethylamine, diethylene triamine,triethylene tetramine, pyridine, piperidine, N,N-diethyl-l,3-propanediamine, dicyandiamide, melamine and fatty acid saltsof amines. However, optimum results have ben obtained by the use of theamine curing or hardening agents and it is preferred to employ saidamines in the preparation of the resinous compositions of thisinvention.

In preparing the resinous compositions of this invention, particularlyfor the purpose of making coverings for surfaces which will receiveexcessive wear, other constituents may be added, as, for example,Portland cement, sand blasting grit, magnesite (calcined magnesiumcarbonate), silica sand, marble chips, non-ferrous metal filings and thelike. Furthermore, many compounds may be added to the resinouscomposition as extenders where reduction in cost is desirable and forthe purpose of facilitating the workability of the resinous composition.It is emphasized that these compounds do not impart elastomericproperties to the composition, i.e. their incorporation, will not resultin a composition having the characteristics of an elastomer, unless themixture of saccharides is present. Such compounds, which willhereinafter be designated as plasticizers, may be liquid petrolatums;mineral oil or white oils; vegetable oils such as olive, corn, peanutand cotton seed oils; neatsfoot oil; and glycols such as ethyleneglycol, diethylene glycol, propylene glycol, triethylene glycol,trimethylene glycol and dipropylene glycol. They may also include thephthalic anhydrideesters such as dibutyl phthalate, diethyl phthalate,dicapryl phthalate, dimethyl phthalate, dioctyl phthalate, butyl benzylphthalate, diisooctyl phthalate, and didecyl phthalate; phosphoric acidesters, such as tricresyl phosphate, triphenyl phosphate, cresylphosphate and alkylaryl phosphates; sebacic acid esters such as dioctylsebacatate, dibutyl sebacatate, diamyl sebacate, dicapryl sebacate,dimethyl sebacate, diiosoctyl sebacate and sebacic acid esters of thecellosolves; adipic acid esters such as dioctyl adipate, diiosoctyladipate, di-Z-ethylhexyl adipate and the adipic acid esters of thecellosolves and polyhydric alcohols; oleic acid esters such asdiethylene glycol mono-oleate, glyceryl mono-oleate including lauricacid esters of methyl and butyl alcohols and of glycols and cellosolves;stearic acid esters such as butyl stearate, diethylene glycolmonostearate, ethylene glycol monostearate, glyceryl monostearate andl,2-propylene monostearate; and dioctyl azelate.

It has been found, surprisingly, that the use of dextrose alone with aresinous epoxide and a hardening agent did not produce an elastomericproduct. In fact, it produced a hard crystalline epoxy resin having aRockwell hardness of M80 to M88. The use of maltose alone with aresinous epoxide and a hardening agent also resulted in a crystallineepoxy resin which was softer than the epoxy resin containing sucrose,i.e. the maltose containing epoxy resin had a hardness of from M to M30.The resinous compositions produced from a resinous epoxide, a hardenerand a mixture of saccharides all had elastomeric characteristics andwere too soft to be measured by a Rockwell hardness tester. Accordingly,a Shore Type A Durometer was employed to test the elastomeric compoundsand the readings obtained on said testing device ranged from about 40 toabout 90. Moreover, when working with resinous epoxides in appreciablequantities and hardening agents, in the absence of saccharide mixtures,undesirable results are obtained. Thus, when working with a batch of 400grams of a resinous epoxide, prepared by reacting 4,4'-dihydroxydiphenyl dimethyl methane with epichlorhydrin, and 10% by weight ofhardener the maximum exotherm is 397 F., the pot life of the epoxy resinproduced is from 15 to 17 minutes, and is discolored. Increasing thebatch to twice the size with respect to said resinous epoxide andhardening agent results in foaming and smoking and the product is quitecharred, unless refrigeration is resorted to. Thus, with large batchesof epoxy resins, without the use of the saccharide mixture of thisinvention, the exotherm is very high, the pot life is of extremely shortduration, and hardening takes place almost instantaneously when thehardening agent is added to the resinous epoxide. It will beappreciated, therefore, that the use of epoxy resins in the preparationof floors and other surface coverings where large batches are requiredis not feasible Where the epoxy resins are not modified by the mixtureof saccharides such as employed in accordance with this invention.

The following examples in which parts are by weight are given to furtherillustrate this invention:

Example I 30 ounces of an epoxy resin prepared by condensing4,4-dihydroxy diphenyl dimethyl methane with epichlorhydrin is mixedwith 2.3 ounces of molasses and 1.8 ounces of triethylene tetramine in avessel at room temperature until a substantially homogeneous liquid isobtained. The peak exothermic temperature during the mixing was 234 F.

The mixture set to an elastomeric solid mass having the followingproperties: 1) flexible, (2) pliable, (3) a Shore type Durometer readingof 83.

Example II 40 ounces of an epoxy resin prepared by condensing4,4'-dihydroxy diphenyl dimethyl methane with epichlorhydrin is mixedwith 5.6 ounces of molasses and 3.2 ounces of triethylene tetramine in avessel at room temperature until a substantially homogeneous liquid isobtained. The peak exothermic temperature during the mixing was 242 F.

The mixture set to an elastomeric solid mass having the followingproperties: (1) flexible, (2) pliable, (3) a Shore type Durometerreading of 71.

Example III 40 ounces of an epoxy resin prepared by condensing4,4'-dihydroxy diphenyl dimethyl methane with epichlorhydrin is mixedwith 3.2 ounces of molasses and 2.4 ounces of triethylene tetramine in avessel at room temperature until a substantially homogeneous liquid isobtained. The peak exothermic temperature during the mixing was 246 F.

The mixture set to an elastomeric solid mass having the followingproperties: (1) having substantially all of the characteristics ofnatural or synthetic rubber, (2) a Shore type Durometer reading of 71.

Example IV 40 ounces of an epoxy resin prepared by condensing4,4-dihydroxy diphenyl dimethyl methane with epichlorhydrin is mixedwith 5.6 ounces of Karo syrup and 4.0 ounces of triethylene tetramine ina vessel at room temperature until a substantially homogeneous liquid isobtained. The peak exothermic temperature during the mixing was 248 F.

The mixture set to an elastomeric solid mass having the followingproperties: (1) flexible, (2) pliable, (3) a Shore type Durometerreading of 81.

Example V 40 ounces of an epoxy resin prepared by condensing4,4'-dihydroxy diphenyl dimethyl methane with epichlorhydrin is mixedwith 5.6 ounces of Karo syrup and 3.0 ounces of triethylene tetramine ina vessel at room temperature until a substantially homogeneous liquid isobtained. The peak exothermic temperature during the mixing was 242 F.

The mixture set to an elastomeric solid mass having the followingproperties: (1) flexible, (2) pliable, (3) a Shore type Durometerreading of 65.

Example VI 40 ounces of an epoxy resin prepared by condensing4,4'-dihydroxy diphenyl dimethyl methane with epichlorhydrin is mixedwith 3.2 ounces of dextrins and 3.2 ounces of triethylene tetramine in avessel at room temperature until a substantially homogeneous liquid isobtained. The peak exothermic temperature during the mixing was 242 F.

The mixture set to an elastomeric solid mass having the followingproperties: (1) having substantially all of the characteristics ofnatural or synthetic rubber, (2) a Shore type Durometer reading of 43.

Example VII 40 ounces of an epoxy resin prepared by condensing4,4-dihydroxy diphenyl dimethyl methane with epichlorhydrin is mixedwith 3.7 ounces of a mixture of equal parts of dextrins and maltose and3.2 ounces of triethylene tetramine in a vessel at room temperatureuntil a substantially homogeneous liquid is obtained. The peakexothermic temperature during the mixing was 245 F.

The mixture set to an elastomeric solid mass having the followingproperties: (1) having substantially all of the characteristics ofnatural or synthetic rubber, (2) a Shore type Durometer reading of 47.

The mixtures in all of the examples given above set on harden in from 4to 18 hours depending upon the temperature and humidity of the ambientatmosphere; the higher the temperature and the lower the humidity, thefaster the rate of hardening, and the lower the temperature and thehigher the humidity, the slower the rate of hardening. Thus, all of theforegoing resinous compounds are eminently suitable for use in thelaying of floors or in the building of wall surfaces. In connection withthe preparation of floor or wall coverings, the fillers and plasticizersare added in quantities sufiicient to give the results desired.Preferably, the solid fillers are added in amounts of from three to fivetimes the weight of the resinous material depending on the resiliencydesired and/ or use to which the covering is to be subjected. Theplasticizer is added in amounts of about based on the weight of theresinous compounds.

It is to be understood that the foregoing detailed description is givenmerely by way of illustration and that many variations may be madetherein without departing from the spirit of my invention.

Having described my invention what I desire to secure by Letters Patentis:

1. Process for the production having the properties of an elastomer,

of synthetic compositions which comprises mixing together a resinousepoxide prepared by reacting dihydroxy diphenyl dimethyl methane withepichlorhydrin, a curing agent and a mixture of dextrins, maltose anddextrose at atmospheric temperature.

2. Process for the production of synthetic resin compositions having theproperties of an elastomer, which comprises mixing together a resinousepoxide prepared by reacting 4,4'-dihydroxy diphenyl dimethyl methanewith epichlorhydrin, tn'ethylene tetramine as curing agent and a mixtureof dextrins, maltose and dextrose at atmospheric temperature.

3. Process for the production of synthetic resin compositions having theproperties of an elastomer, Which comprises mixing together a resinousepoxide prepared by reacting dihydroxy diphenyl dimethyl methane withepichlorhydrin, from 7 to 15% by weight of the resinous epoxide of acuring agent, and from 6 to 10% by weight of the resinous epoxide of amixture of dextrins, maltose and dextrose at atmospheric temperature.

4. A non-aqueous resinous composition comprising a resinous epoxideprepared by reacting dihydroxy diphenyl dimethyl methane withepichlorhydrin, a curing agent and a mixture of dextrins, maltose anddextrose.

5. A non-aqueous resinous composition comprising a resinous epoxideprepared by reacting 4,4'-dihydroxy diphenyl dimethyl methane withepichlorhydrin, triethylene tetramine as curing agent and a mixture ofdextrins, maltose and dextrose.

6. A non-aqueous resinous composition comprising a resinous epoxideprepared by reacting dihydroxy diphenyl dimethyl methane withepichlorhydrin, from 7 to 15% by weight of the resinous epoxide of acuring agent, and from 6 to 10% by weight of the resinous epoxide of amixture of dextrins, maltose and dextrose.

7. A protective covering to be applied to a surface comprising aresinous epoxide prepared by reacting dihydroxy diphenyl dimethylmethane with epichlorhydrin, a curing agent, a mixture of dextrins,maltose and dextrose, and a particulate filler.

8. A protective covering to be applied to a surface comprising aresinous epoxide prepared by reacting 4,4'- dihydroxy diphenyl dimethylmethane with epichlorhydrin, triethylene tetramine as curing agent, amixture of dextrins, maltose and dextrose, and a particulate filler.

9. A protective covering to be applied to a surface comprising aresinous epoxide prepared by reacting dihydroxy diphenyl dimethylmethane with epichlorhydrin, from 7 to 15% by weight of the resinousepoxide of a curing agent, and from 6 to 10% by weight of the resinousepoxide of a mixture of dextrins, maltose and dextrose, and aparticulate filler.

References Cited in the file of this patent UNITED STATES PATENTS2,512,996 Bixler June 27, 1950 2,682,515 Naps June 29, 1954 2,811,495Witcoif Oct. 29, 1957

1. PROCESS FOR THE PRODUCTION OF SYNTHETIC COMPOSITIONS HAVING THEPROPERTIES OF AN ELASTOMER, WHICH COMPRISES MIXING TOGETHER A RESINOUSEPOXIDE PREPARED BY REACTING DIHYDROXY DIPHENYL DIMETHYL METHANE WITHEPICHLORHYDRIN, A CURING AGENT AND A MIXTURE OF DEXTRINS, MALTOSE ANDDEXTROSE AT ATMOSPHERIC TEMPERATURE.